US3272853A - Metal chelates containing perhaloalkyl groups - Google Patents
Metal chelates containing perhaloalkyl groups Download PDFInfo
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- US3272853A US3272853A US271579A US27157963A US3272853A US 3272853 A US3272853 A US 3272853A US 271579 A US271579 A US 271579A US 27157963 A US27157963 A US 27157963A US 3272853 A US3272853 A US 3272853A
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G59/00—Polycondensates containing more than one epoxy group per molecule; Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups
- C08G59/18—Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups ; e.g. general methods of curing
- C08G59/68—Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups ; e.g. general methods of curing characterised by the catalysts used
- C08G59/70—Chelates
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C49/00—Ketones; Ketenes; Dimeric ketenes; Ketonic chelates
- C07C49/92—Ketonic chelates
Definitions
- X is an alkyl radical containing 1 through 5 carbon atoms; a perchloro-, perfiuoro-, or mixed perchlorofiuoroalkyl radical containing 1 through 5 carbon atoms; an aryl radical; an aryl radical substituted with OCH Cl, CH or NO or a thienyl radical;
- D is X or OX
- M is a metal having a valence of 2 through 4;
- n is a number 1 through 4.
- n is a number 0-3;
- n+m cannot exceed the valence of the metal.
- perchloro-fluoroalkyl such radicals as CF CF Cl, C F- -C F CC1 --CCl F, C2F5, C4F9, and CFC12.
- the metals having valences of from 2 to 4 include copper, nickel, iron, magnesium, cobalt, chromium, zirconium, manganese, indium, vanadium, and beryllium.
- UTILITY Chelates of Formula 1 are useful as catalysts for the polymerization of diand polyepoxides. In the preparation of such polymers, they can be used as catalysts in concentrations of from 0.1 to 5%, by weight, of the reactants. Polymerizations are carried out according to customary methods; use of these chelates as catalysts requires no new techniques or processing.
- the chelates are also useful in the same applications as the parent chelates. For example, they can be used as catalysts for the oxidation of hydrocarbons, and as stabilizers for polymers.
- the chelates of this invention are better than the parent compounds for these purposes because they are more soluble in organic solvents.
- Preferred for these uses are the compounds of Formula 1 wherein A and A are perfluoromethy'l.
- metal chelates of this invention are prepared by the reaction of a perchloroor perfluoroketone with a metal chelate of a ,B-diketone or a B-keto ester, according to the following equation:
- a A X, D, m and n have the same meanings as in Formula 1.
- the reactants are placed in a closed container such as a stainless steel bomb or a sealed glass tube. They can, if desired, be first dissolved or mixed in a solvent such as benzene, ether, petroleum ether or toluene.
- a solvent such as benzene, ether, petroleum ether or toluene. The solvent is not necessary, but it has been observed that a more uniform reaction takes place if it is present.
- the reaction mass is then heated to a temperature of from 100 to 250 C., preferably ISO-200 C. for from 1-24 hours, preferably 4-8 hours.
- the precise temperature and reaction time will, of course, depend upon the reactants used. Generally speaking, the reaction proceeds quite rapidly.
- the product is recovered by stripping olf the solvent under vacuum or nitrogen. If the reaction is run in the absence of a solvent and the product is a solid, it can be purified by recrystallizing from an organic solvent such as ethyl acetate or benzene. If the product is an oil, it will require no further purification.
- Example I A mixure of cupric acetylacetonate (26.2 grams, 0.1 mole), benzene (50 grams) and hexafiuoroacetone (34 grams, 0.205 mole) was heated in a bomb at 150 C. for four hours.
- the blue crystalline sold was recrystallized from ethyl acetate to give 21.7 grams of blue needles and 1.05 grams of a grey insoluble powder.
- Example 3 A mixture of zirconium acetylacetonate (15.9 grams, 0.0327 mole), benzene (50 grams) and hexafiuoroacetone (20 grams, 0.132 mole) was heated in a stainless steel bomb at 175 C. for six hours.
- Example 4 A mixture of recrystallized nickel acetoacetate (28.5 grams, 0.1 mole), hexafiuoroacetone (37 grams, 0.22 mole) and benzene grams) was heated in a stainless steel bomb at C. for six hours.
- the resulting friable glassy product had the formula
- the following chelates, in equimolar amounts, can be substituted for the cobaltous acetylacetonate and reacted with hexafiuoroacetone in a similar fashion to give the corresponding metal chelates of the invention:
- Hexafluoroacetone can be replaced with equimolar amounts of the following ketones and reacted with cobaltous acetylacetonate in a similar fashion to give the corresponding chelates of the invention:
- X is selected from the group consisting of alkyl radicals containing 1 through 5 carbon atoms; perchloroalkyl, perfluoroalkyl and mixed perchloro-fiuoroalkyl radicals all containing 1 through 5 carbon atoms, aryl radicals; -OCH Cl, -CH and NO;, substituted aryl radicals; and thienyl;
- D is selected from the group consisting of X and -OX;
- M is a metal having a valence of 2-4;
- n is a number 1-4;
- n is a number 0-3;
- a compound according to claim 1 wherein A and A are selected from the group consisting of perfluoromethyl and perchloromethyl.
- a compound of the formula CFa O CIJ CH3 0.. ;C J OH 5.
- a compound of the formula CH3 O CII CF: Ni ⁇ COIOH oo or.
Description
United States Patent O "ice 3,272,853 METAL CHELATES CONTAINING PERHALO- ALKYL GROUPS Robert A. Braun, Newark, Del., assignor to E. I. du Pont do Nemours and Company, Wilmington, DeL, a corporation of Delaware N Drawing. Filed Apr. 9, 1963, Ser. No. 271,579 10 Claims. (Cl. 260-4381) This invention relates to metal chelates and is more particularly directed to metal chelates having the formula A and A are perchloro-, perfluoro-, or mixed perchlorofluoroalkyl radicals containing 1 through carbon atoms;
X is an alkyl radical containing 1 through 5 carbon atoms; a perchloro-, perfiuoro-, or mixed perchlorofiuoroalkyl radical containing 1 through 5 carbon atoms; an aryl radical; an aryl radical substituted with OCH Cl, CH or NO or a thienyl radical;
D is X or OX;
M is a metal having a valence of 2 through 4;
n is a number 1 through 4; and
m is a number 0-3;
provided that n+m cannot exceed the valence of the metal.
By perchloro-fluoroalkyl is meant such radicals as CF CF Cl, C F- -C F CC1 --CCl F, C2F5, C4F9, and CFC12.
The metals having valences of from 2 to 4 include copper, nickel, iron, magnesium, cobalt, chromium, zirconium, manganese, indium, vanadium, and beryllium.
UTILITY Chelates of Formula 1 are useful as catalysts for the polymerization of diand polyepoxides. In the preparation of such polymers, they can be used as catalysts in concentrations of from 0.1 to 5%, by weight, of the reactants. Polymerizations are carried out according to customary methods; use of these chelates as catalysts requires no new techniques or processing.
The chelates are also useful in the same applications as the parent chelates. For example, they can be used as catalysts for the oxidation of hydrocarbons, and as stabilizers for polymers. The chelates of this invention, however, are better than the parent compounds for these purposes because they are more soluble in organic solvents.
Preferred for these uses are the compounds of Formula 1 wherein A and A are perfluoromethy'l.
Especially preferred are those wherein A and A are perfluoromethyl, X is methyl and D is OC H Most preferred are 3,272,853 Patented Sept. 13, 1966 PREPARATION OF COMPOUNDS The metal chelates of this invention are prepared by the reaction of a perchloroor perfluoroketone with a metal chelate of a ,B-diketone or a B-keto ester, according to the following equation:
where A A X, D, m and n have the same meanings as in Formula 1.
In this procedure, the reactants are placed in a closed container such as a stainless steel bomb or a sealed glass tube. They can, if desired, be first dissolved or mixed in a solvent such as benzene, ether, petroleum ether or toluene. The solvent is not necessary, but it has been observed that a more uniform reaction takes place if it is present.
If compounds of Formula 1 where m is are desired, a stoichiometric excess of the ketone reactant is used. If compounds where m is a positive number are desired, m number of moles of metal chelate reactant will be used.
The reaction mass is then heated to a temperature of from 100 to 250 C., preferably ISO-200 C. for from 1-24 hours, preferably 4-8 hours. The precise temperature and reaction time will, of course, depend upon the reactants used. Generally speaking, the reaction proceeds quite rapidly.
If the solvent is used, the product is recovered by stripping olf the solvent under vacuum or nitrogen. If the reaction is run in the absence of a solvent and the product is a solid, it can be purified by recrystallizing from an organic solvent such as ethyl acetate or benzene. If the product is an oil, it will require no further purification.
EXAMPLES The following examples are presented so that the invention may be more readily practiced and easily understood.
Example I A mixure of cupric acetylacetonate (26.2 grams, 0.1 mole), benzene (50 grams) and hexafiuoroacetone (34 grams, 0.205 mole) was heated in a bomb at 150 C. for four hours.
This gave a partially crystalline green material which was filtered and washed with 10 ml. portions of benzene to give 23.8 grams of a blue crystalline solid and a deep green filtrate.
The blue crystalline sold was recrystallized from ethyl acetate to give 21.7 grams of blue needles and 1.05 grams of a grey insoluble powder.
The blue crystals were further purified by two sublimations at 170 C. and 25 mm. of pressure to give a compound having the formula 5 =C\ C F; Cu C-COH O-(il 0 F3 CH3 2 and a melting point of 167 C.
Example 3 A mixture of zirconium acetylacetonate (15.9 grams, 0.0327 mole), benzene (50 grams) and hexafiuoroacetone (20 grams, 0.132 mole) was heated in a stainless steel bomb at 175 C. for six hours.
The solvent was then removed at reduced pressure to give 31.2 grams of a viscous red oil consisting mainly of a compound having the formula 4 Example 4 A mixture of recrystallized nickel acetoacetate (28.5 grams, 0.1 mole), hexafiuoroacetone (37 grams, 0.22 mole) and benzene grams) was heated in a stainless steel bomb at C. for six hours.
The solvent was stripped at 25 C. and 0.1 ml. of pressure to give 59 grams of a viscous green 011 having the Polymerization of Union Carbide Corporations Epoxide 201 having the formula Example 5 A mixture of cobaltous acetylacetonate (0.05 mole), hexafiuoroacetone (0.12 mole) and benzene (300 ml.) was heated in a closed bomb for six hours at ISO- C.
The resulting friable glassy product had the formula The following chelates, in equimolar amounts, can be substituted for the cobaltous acetylacetonate and reacted with hexafiuoroacetone in a similar fashion to give the corresponding metal chelates of the invention:
Hexafluoroacetone can be replaced with equimolar amounts of the following ketones and reacted with cobaltous acetylacetonate in a similar fashion to give the corresponding chelates of the invention:
1,1,3-trifiuoro-1,3 ,3-trichloroacetone 1,1,1-trifluoro-3,3,3-trichloroacetone chloropentafluoroacetone perfiuorohepan-4-one Example 6 Cobalt acetylacetonate (24.2 grams, 0.068 mole) was reacted with hexafiuoroacetone (35 grams, 0.21 mole) in a bomb for six hours at ISO-160 C. to give a dark green ether-soluble glassy resin which resisted recrystallization. This resin had the formula Equimolar quantities of the following reactants can be used in place of cobalt acetylacetonate and reacted with hexafiuoroacetone in a similar fashion to give the corresponding metal chelates of the invention:
ferric ethyl acetoacetate chromium hexafluoroacetyl acetonate vanadium trifluoroacetyl acetonate indium acetylacetonate aluminum thienoyl acetonate Example 7 A mixture of magnesium acetylacetonate (20 grams, 0.09 mole), hexafluoroacetone (37 grams, 0.22 mole) and benzene (50 ml.) was heated for six hours at 150 C. to give 14.7 grams of a light, tan benzene-insoluble solid and a tacky, amber, benzene and ether-soluble resin.
Long air drying of the benzene-insoluble solid gave 18 grams of a solid which was only partially soluble in benzene.
An extraction of this solid with benzene gave an insoluble fraction (5.2 grams) having a melting point of 184 C. After oven drying, this product melted only partially at 224 C. It had the formula The embodiments of the invention in which an exclusive property or privilege is claimed are:
1. A compound having the formula where A and A are selected from the group consisting of perchloroalkyl, perfluoroalkyl and mixed perchlorofiuoroalkyl radicals all containing 1 through 5 carbon atoms;
X is selected from the group consisting of alkyl radicals containing 1 through 5 carbon atoms; perchloroalkyl, perfluoroalkyl and mixed perchloro-fiuoroalkyl radicals all containing 1 through 5 carbon atoms, aryl radicals; -OCH Cl, -CH and NO;, substituted aryl radicals; and thienyl;
D is selected from the group consisting of X and -OX;
M is a metal having a valence of 2-4;
n is a number 1-4; and
m is a number 0-3;
provided, however, that the sum of n and m cannot exceed the valence number of the metal.
2. A compound according to claim 1, wherein A and A are selected from the group consisting of perfluoromethyl and perchloromethyl.
3. A compound according to claim 1, wherein A and A are selected from the group consisting of perchloromethyl and perfluoromethyl; X is methyl and D is OC H 4. A compound of the formula CFa O=CIJ CH3 0.. ;C J OH 5. A compound of the formula CH3 o( 3 (3E3 Co 6 O OH 00 on (1H, 2 6. A compound of the formula CH3 O(|J CF Co o- I -OH 00 JF CH 3 7. A compound of the formula CF: 0(': or. Ni \C-(|JOH 0o CF3 (IlFa 2 8. A compound of the formula CH3 O=CII CF: Ni \COIOH oo or.
9. A compound of the formula CH3 oo 01?, Fe ;o {-011 o-o CF; CH. 3
10. A compound of the formula CH3 O=(J CFg Mg ;C-C:OH
O-G C'Fa 6H. 2
References Cited by the Examiner UNITED STATES PATENTS 3,014,939 12/1961 Kluiber 260-429 OTHER REFERENCES Belford et al.: (I) J. Inorg. and Nuc. Chem., vol. 2, 1956, pp. 11-31.
Belford et 211.: (H) J. Inorg. and Nuc. Chem, vol. 14, 1960, pp. 169-178.
T OBIAS E. LEVOW, Primary Examiner.
E. C. BARTLETT, H. M. SNEED, Assistant Examiners.
Claims (2)
1. A COMPOUND HAVING THE FORMULA
4. A COMPOUND OF THE FORMULA
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| US271579A US3272853A (en) | 1963-04-09 | 1963-04-09 | Metal chelates containing perhaloalkyl groups |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| US271579A US3272853A (en) | 1963-04-09 | 1963-04-09 | Metal chelates containing perhaloalkyl groups |
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| Publication Number | Publication Date |
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| US3272853A true US3272853A (en) | 1966-09-13 |
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| Application Number | Title | Priority Date | Filing Date |
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| US271579A Expired - Lifetime US3272853A (en) | 1963-04-09 | 1963-04-09 | Metal chelates containing perhaloalkyl groups |
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Cited By (10)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US3393178A (en) * | 1965-03-18 | 1968-07-16 | Interchem Corp | Zinc chelate and polyepoxide compositions containing it |
| US3547582A (en) * | 1966-08-30 | 1970-12-15 | Nippon Steel Corp | Method for manufacture of high purity iron oxide powder |
| US3617388A (en) * | 1966-07-25 | 1971-11-02 | Monsanto Res Corp | Method of activating fuel cell anodes |
| US3626022A (en) * | 1967-04-13 | 1971-12-07 | Asahi Denka Kogyo Kk | Hardenable epoxy resin containing chelates from metal halides, monoepoxides, and chelate forming compounds |
| US3692738A (en) * | 1971-04-08 | 1972-09-19 | Phillips Petroleum Co | Ultraviolet stabilizer system for polyolefins |
| US4150047A (en) * | 1978-03-06 | 1979-04-17 | Air Products And Chemicals, Inc. | Process for preparing halogenated metal chelates |
| US4157975A (en) * | 1974-06-21 | 1979-06-12 | Agence Nationale De Valorisation De La Recherche (Anvar) | Electrical insulators having increased resistance to partial discharges |
| US4425281A (en) | 1981-07-13 | 1984-01-10 | Exxon Research And Engineering Co. | Copper or silver complexes with fluorinated diketones and unsaturated ligands |
| US4845254A (en) * | 1987-08-07 | 1989-07-04 | Air Products And Chemicals, Inc. | Novel metal-diketone absorbents for carbon monoxide or olefins |
| CN114524914A (en) * | 2022-03-11 | 2022-05-24 | 广州优润合成材料有限公司 | Reactive low-volatility beta dicarbonyl coordination metal catalyst and preparation method thereof |
Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US3014939A (en) * | 1960-07-01 | 1961-12-26 | Union Carbide Corp | Halogenated metal chelates |
-
1963
- 1963-04-09 US US271579A patent/US3272853A/en not_active Expired - Lifetime
Patent Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US3014939A (en) * | 1960-07-01 | 1961-12-26 | Union Carbide Corp | Halogenated metal chelates |
Cited By (10)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US3393178A (en) * | 1965-03-18 | 1968-07-16 | Interchem Corp | Zinc chelate and polyepoxide compositions containing it |
| US3617388A (en) * | 1966-07-25 | 1971-11-02 | Monsanto Res Corp | Method of activating fuel cell anodes |
| US3547582A (en) * | 1966-08-30 | 1970-12-15 | Nippon Steel Corp | Method for manufacture of high purity iron oxide powder |
| US3626022A (en) * | 1967-04-13 | 1971-12-07 | Asahi Denka Kogyo Kk | Hardenable epoxy resin containing chelates from metal halides, monoepoxides, and chelate forming compounds |
| US3692738A (en) * | 1971-04-08 | 1972-09-19 | Phillips Petroleum Co | Ultraviolet stabilizer system for polyolefins |
| US4157975A (en) * | 1974-06-21 | 1979-06-12 | Agence Nationale De Valorisation De La Recherche (Anvar) | Electrical insulators having increased resistance to partial discharges |
| US4150047A (en) * | 1978-03-06 | 1979-04-17 | Air Products And Chemicals, Inc. | Process for preparing halogenated metal chelates |
| US4425281A (en) | 1981-07-13 | 1984-01-10 | Exxon Research And Engineering Co. | Copper or silver complexes with fluorinated diketones and unsaturated ligands |
| US4845254A (en) * | 1987-08-07 | 1989-07-04 | Air Products And Chemicals, Inc. | Novel metal-diketone absorbents for carbon monoxide or olefins |
| CN114524914A (en) * | 2022-03-11 | 2022-05-24 | 广州优润合成材料有限公司 | Reactive low-volatility beta dicarbonyl coordination metal catalyst and preparation method thereof |
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